Different Aspects of Single Wall Carbon Nanotube Functionalization by Aniline Adsorption; Quantum Mechanics/Molecular Mechanics Study

Abstract:

In this research, kinetics and mechanism of aniline adsorption on different single-walled carbon nanotubes (SWCNT) was investigated, using 2-layer ONIOM (Our own N-layered Integrated molecular Orbital and molecular Mechanics) method at the ONIOM (B3LYP/6-31G (d);UFF) level. Various orientations of aniline relative to the carbon nanotube surface were investigated. To investigate the adsorption of aniline, three models including open-ended (model 1), cap-ended (model 2) and 1-cap-ended (model 3) SWCNT have been modeled. Calculated activation energies of adsorption showed that model 2 has the lowest activation energy of 40.8 kcal.mol^-1. Natural bond orbital and frontier molecular orbital analysis confirmed the charge transfer from the aniline to the SWCNT. Density of states analysis showed that Fermi level is shifted towards the positive values after aniline adsorption which confirmed the effective interactions between the aniline and the SWCNT. According to the quantum theory of atoms in molecules studies, new bonds formed between the SWCNT and aniline which possess a covalence nature. Finally, based on the quantum reactivity indices, new linear correlations between the chemical hardness, charge transfer and activation energy and the inverse relationship of the electrophilic property and chemical electronic potential in the functionalized carbon nanotubes were obtained. Wiberg bond index calculations show that this reaction is carried out through an asynchronous concerted mechanism. Asynchronicity value in the case of model 2 is higher than other models.

• Periodical: Journal of Nano Research (Volume 32)
• Pages: 1-16
• DOI: https://doi.org/10.4028/www.scientific.net/JNanoR.32.1
• Online since: May 2015
• Authors: Mohamood Abedini, Mohammad Izadyar*, Ali Nakhaeipour
• Keywords: Adsorption, Aniline, Carbon Nanotube, Functionalization, Mechanism, ONIOM

References

[1] C.H. Li, Recovery of aniline from wastewater by nitrobenzene extraction enhanced with salting-out effect. Biomedical and Environmental Sciences 2010, 23 (3), 208-212.

DOI: 10.1016/s0895-3988(10)60054-2

[2] S. P. Kamble, S. B. Sawant, J. C. Schouten, V. G. Pangarkar, Photocatalytic and photochemical degradation of aniline using concentrated solar radiation. Journal of Chemical Technology and Biotechnology 2003, 78 (8), 865-872.

DOI: 10.1002/jctb.867

[3] J. Li, Z. Jin, Effect of hypersaline aniline-containing pharmaceutical wastewater on the structure of activated sludge-derived bacterial community. Journal of hazardous materials 2009, 172 (1), 432-438.

DOI: 10.1016/j.jhazmat.2009.07.031

[4] W. Chu, W. Chou, T. So, The effect of solution pH and peroxide in the TiO2 induced photocatalysis of chlorinated aniline. Journal of hazardous materials 2007, 141 (1), 86-91.

DOI: 10.1016/j.jhazmat.2006.06.093

[5] C. Karunakaran, S. Senthilvelan, Solar photocatalysis: oxidation of aniline on CdS. Solar energy 2005, 79 (5), 505-512.

DOI: 10.1016/j.solener.2004.12.004

[6] A. Kumar, N. Mathur, Photocatalytic degradation of aniline at the interface of TiO2 suspensions containing carbonate ions. Journal of colloid and interface science 2006, 300 (1), 244-252.

DOI: 10.1016/j.jcis.2006.03.046

[7] Y. Han, X. Quan, S. Chen, H. Zhao, C. Cui, Y. Zhao, Electrochemically enhanced adsorption of aniline on activated carbon fibers. Separation and purification technology 2006, 50 (3), 365-372.

DOI: 10.1016/j.seppur.2005.12.011

[8] N. Jagtap, V. Ramaswamy, Oxidation of aniline over Titania pillared montmorillonite clays, Applied clay science 2006, 33 (2), 89-98.

DOI: 10.1016/j.clay.2006.04.001

[9] H. Gomes, P. Selvam, S. Dapurkar, J. Figueiredo, J. Faria, Transition metal (Cu, Cr, and V) modified MCM-41 for the catalytic wet air oxidation of aniline. Microporous and mesoporous materials 2005, 86 (1), 287-294.

DOI: 10.1016/j.micromeso.2005.07.022

[10] L. Wang, S. Barrington, J. W. Kim, Biodegradation of pentyl amine and aniline from petrochemical wastewater. Journal of environmental management 2007, 83 (2), 191-197.

DOI: 10.1016/j.jenvman.2006.02.009

[11] Q. Zhou, J. Xiao, W. Wang, Using multi-walled carbon nanotubes as solid phase extraction adsorbents to determine dichlorodiphenyltrichloroethane and its metabolites at trace level in water samples by high performance liquid chromatography with UV detection. Journal of Chromatography A 2006, 1125 (2), 152-158.

DOI: 10.1016/j.chroma.2006.05.047

[12] Q. Zhou, W. Wang, J. Xiao, Preconcentration and determination of nicosulfuron, thifensulfuron-methyl and metsulfuron-methyl in water samples using carbon nanotubes packed cartridge in combination with high performance liquid chromatography. Analytica chimica acta 2006, 559 (2), 200-206.

DOI: 10.1016/j.aca.2005.11.079

[13] M. A. Salam, R. Burk, Novel application of modified multiwalled carbon nanotubes as a solid phase extraction adsorbent for the determination of polyhalogenated organic pollutants in aqueous solution. Analytical and Bioanalytical Chemistry 2008, 390 (8), 2159-2170.

DOI: 10.1007/s00216-008-1960-9

[14] M. A. Salam, R. Burk, Solid phase extraction of polyhalogenated pollutants from freshwater using chemically modified multi‐walled carbon nanotubes and their determination by gas chromatography. Journal of Separation Science 2009, 32 (7), 1060-1068.

DOI: 10.1002/jssc.200800593

[15] G. Sheng, D. Shao, X. Ren, X. Wang, J. Li, Y. Chen, X. Wang, Kinetics and thermodynamics of adsorption of ionizable aromatic compounds from aqueous solutions by as-prepared and oxidized multiwalled carbon nanotubes. Journal of hazardous materials 2010, 178 (1), 505-516.

DOI: 10.1016/j.jhazmat.2010.01.110

[16] A. K. Rappé, C. J. Casewit, K. Colwell, Iii, W. Goddard, W. Skiff, UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations. Journal of the American Chemical Society 1992, 114 (25), 10024-10035.

DOI: 10.1021/ja00051a040

[17] A. D. Becke, Density-functional exchange-energy approximation with correct asymptotic behavior. Physical Review A 1988, 38 (6), 3098.

DOI: 10.1103/physreva.38.3098

[18] C. Lee, W. Yang, R. G. Parr, Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Physical Review B 1988, 37 (2), 785.

DOI: 10.1103/physrevb.37.785

[19] B. Miehlich, A. Savin, H. Stoll, H. Preuss, Results obtained with the correlation energy density functionals of Becke and Lee, Yang and Parr. Chemical Physics Letters 1989, 157 (3), 200-206.

DOI: 10.1016/0009-2614(89)87234-3

[20] G. Petersson, M. A. Al-Laham, A complete basis set model chemistry. II. Open-shell systems and the total energies of the first-row atoms. The Journal of chemical physics 1991, 94, 6081.

DOI: 10.1063/1.460447

[21] M.J. Frisch, G. W. T., H.B. Schlegel, G.E. Scuseria, M.A.; Robb, J. R. C., J.A. Montgomery, T. Vreven, K.N. Kudin,; J.C. Burant, J. M. M., S.S. Iyengar, J. Tomasi, V. Barone,; B. Mennucci, M. C., G. Scalmani, N. Rega, G.A. Petersson, H.; Nakatsuji, M. H., M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa,; M. Ishida, T. N., Y. Honda, O. Kitao, H. Nakai, M.; Klene, X. L., J.E. Knox, H.P. Hratchian, J.B. Cross, V. Bakken,; C. Adamo, J. J., R. Gomperts, R.E. Stratmann, O. Yazyev,; A.J. Austin, R. C., C. Pomelli, J.W. Ochterski, P.Y.; Ayala, K. M., G.A. Voth, P. Salvador, J.J. Dannenberg,; V.G. Zakrzewski, S. D., A.D. Daniels, M.C. Strain, O.; Farkas, D. K. M., A.D. Rabuck, K. Raghavachari, J.B.; Foresman, J. V. O., Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski,; B.B. Stefanov,G. L., A. Liashenko, P. Piskorz, I.; Komaromi, R. L. M., D.J. Fox, T. Keith, M.A. Al-Laham,; C.Y. Peng,A. N., M. Challacombe, P.M.W. Gill, B.; Johnson, W. C., M.W. Wong, C. Gonzalez, J.A. Pople, Gaussian 03, Revision B. 03 (Gaussian. Inc., Wallingford, CT, 2004). (2004).

[22] Dennington, R. K., Todd; Millam, John. Semichem Inc., Shawnee Mission, KS, , GaussView, Version 5. (2009).

[23] A. E. Reed, L. A. Curtiss, F. Weinhold, Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint. Chemical Reviews 1988, 88 (6), 899-926.

DOI: 10.1021/cr00088a005

[24] A. E. Reed, F. Weinhold, Natural bond orbital analysis of near‐Hartree–Fock water dimer. The Journal of chemical physics 1983, 78 (6), 4066-4073.

DOI: 10.1063/1.445134

[25] R. F. Bader, W. A. i. M., A Quantum Theory; Oxford; University Press: New York, Atoms in Molecules, A Quantum Theory. (1990).

[26] R. F. Bader, W. A. P. M. U.; Hamilton, O., Canada, 2000., AIM 2000 Program. (2000).

[27] C. Peng, P. Y. Ayala, H. B. Schlegel, M. J. Frisch, Using redundant internal coordinates to optimize equilibrium geometries and transition states; Journal of Computational Chemistry 1996, 17, (1), 49-56.

DOI: 10.1002/(sici)1096-987x(19960115)17:1<49::aid-jcc5>3.0.co;2-0

[28] H. Aljohani, M. A. Salam, Kinetics and thermodynamic study of aniline adsorption by multi-walled carbon nanotubes from aqueous solution; Journal of Colloid and Interface Science 2011, 360, (2), 760-767.

DOI: 10.1016/j.jcis.2011.04.097

[29] B. G. Oliveira, Interplay between dihydrogen and alkali-halogen bonds: is there some covalency upon complexation of ternary systems? Computational and Theoretical Chemistry (2012).

DOI: 10.1016/j.comptc.2012.07.031

[30] A. Moyano, M. A. Pericas, E. Valenti, A theoretical study on the mechanism of the thermal and the acid-catalyzed decarboxylation of 2-oxetanones (. beta. -lactones); The Journal of Organic Chemistry 1989, 54, (3), 573-582.

DOI: 10.1021/jo00264a014

[31] M. J. Dewar, Multibond reactions cannot normally be synchronous; Journal of the American Chemical Society 1984, 106, (1), 209-219.

DOI: 10.1021/ja00313a042

[32] T. Vreven, k. Morokuma, Hybrid Methods: ONIOM(QM: MM) and QM/MM, Annual Reports in Competational Chemistry 2 (2006) 35-51.

DOI: 10.1016/s1574-1400(06)02003-2

[33] T, Vreven, K. S. Byun, I. Komaromi, S. Dapprich, J. A. Montgomery, K. Morokuma, M. J. Frisch, Combining Quantum Mechanics Methods with Molecular MechanicsMethods in ONIOM, Journal of Chem. Theory and Computation 2 (2006) 815-26.

DOI: 10.1021/ct050289g